Group 11 complexes with unsymmetrical P,S and P,Se disubstituted ferrocene ligands

Article abstract of DOI:10.1039/b507058a

The reaction of the unsymmetrical ligands l-diphenylphosphino-1′-(phenylsulfanyl)ferrocene and 1-diphenylphosphino-1′-(phenylselenyl)ferrocene, Fc(EPh)PPh₂ (E = S, Se), with several group 11 metal derivatives leads to the synthesis of complexes of the type [MX{Fc(EPh)PPh₂}] (M = Au, X = Cl, C ₆F₅; M = Ag, X = OTf), (OTf = trifluoromethanesulfonate), [M{Fc(EPh)PPh₂}₂]X (M = Au, X = ClO₄; M = Ag, X = OTf), [M(PPh₃){Fc(EPh)PPh₂}]OTf (M = Au, Ag), [Au ₂{Fc(SPh)PPh₂}₂](ClO₄)₂, [Au(C₆F₅)₂{Fc(SePh)PPh₂}]ClO ₄, [Au(C₆F₅)₃{Fc(EPh)PPh ₂}], [Au₂(C₆F₅) ₆{Fc(SePh)PPh₂}] or [Cu{Fc(EPh)PPh₂} ₂]PF₆ (E = S, Se). In these complexes coordination depends upon the metal centre; with gold it takes place predominantly to the phosphorus atom and with silver and copper to both phosphorus and chalcogen atoms. The treatment of some of the gold complexes with other metal centres affords heterometallic derivatives that in some cases are in equilibrium with the homometallic derivatives. Several compounds have been characterized by X-ray diffraction, four pairs of homologous compounds, yet not a single pair is isotypic. In many of them a three dimensional network is formed through secondary bonds such as hydrogen bonds, Au ... Cl or Au ... Se interactions. The complex [Ag(OTf){Fc(SePh)PPh₂}] forms one-dimensional chains through trifluoromethanesulfonate bridging ligands. The Royal Society of Chemistry 2005.

Full text of DOI:10.1039/b507058a

View Article Online / Journal Homepage / Table of Contents for this issue
F U L L P A P E R
Group 11 complexes with unsymmetrical P,S and P,Se disubstituted
ferrocene ligands
Javier E. Aguado,a Silvia Canales,a M. Concepcio´n Gimeno,*a Peter G. Jones,b
Antonio Lagunaa and M. Dolores Villacampaa
a Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain
b Institut fu¨r Anorganische und Analytische Chemie der Technischen Universita¨t, Postfach 3329,
D-38023 Braunschweig, Germany
Received 18th May 2005, Accepted 6th July 2005
First published as an Advance Article on the web 4th August 2005
The reaction of the unsymmetrical ligands 1-diphenylphosphino-1ꢀ-(phenylsulfanyl)ferrocene and
1-diphenylphosphino-1ꢀ-(phenylselenyl)ferrocene, Fc(EPh)PPh2 (E = S, Se), with several group 11 metal
derivatives leads to the synthesis of complexes of the type [MX{Fc(EPh)PPh2}] (M = Au, X = Cl, C6F5; M = Ag,
X = OTf), (OTf = trifluoromethanesulfonate), [M{Fc(EPh)PPh2}2]X (M = Au, X = ClO4; M = Ag, X = OTf),
[M(PPh3){Fc(EPh)PPh2}]OTf (M = Au, Ag), [Au2{Fc(SPh)PPh2}2](ClO4)2, [Au(C6F5)2{Fc(SePh)PPh2}]ClO4,
[Au(C6F5)3{Fc(EPh)PPh2}], [Au2(C6F5)6{Fc(SePh)PPh2}] or [Cu{Fc(EPh)PPh2}2]PF6 (E = S, Se). In these complexes
coordination depends upon the metal centre; with gold it takes place predominantly to the phosphorus atom and
with silver and copper to both phosphorus and chalcogen atoms. The treatment of some of the gold complexes with
other metal centres affords heterometallic derivatives that in some cases are in equilibrium with the homometallic
derivatives. Several compounds have been characterized by X-ray diffraction, four pairs of homologous compounds,
yet not a single pair is isotypic. In many of them a three dimensional network is formed through secondary bonds
such as hydrogen bonds, Au · · · Cl or Au · · · Se interactions. The complex [Ag(OTf){Fc(SePh)PPh2}] forms
one-dimensional chains through trifluoromethanesulfonate bridging ligands.
As part of our studies of ferrocene derivatives as ligands,26
Introduction
we report here on the synthesis of the first unsymmetrical
The chemistry of ferrocene-containing compounds has received
ferrocenyl ligand having both P and Se as donor atoms and
considerable attention in recent years, associated with the utility
on the reactivity of the Fc(SPh)PPh2 and Fc(SePh)PPh2 ligands
of such products in many fields such as organic synthesis, catal-
with group 11 metal complexes. The reactivity of the three
ysis or materials chemistry.1–3 In these complexes the inherent
metals is different; gold predominantly coordinates through the
properties of the ferrocene moiety such as its high stability
phosphorus donor ligand, silver can coordinate either through
and reversible redox character, have played an important role in
the phosphorus only or through both donor atoms (phosphorus
coordination chemistry. The functionalization of the cyclopenta-
and chalcogen), and copper coordinates to both donor atoms.
dienyl rings with various donor groups and subsequent ligation
Some heteronuclear complexes have been prepared starting from
to metal centres are an important topic of research in many
the gold complexes. The crystal structure determinations of
fields that seek special properties of such species, for example
some of the gold and silver complexes provide experimental
non-linear optical properties, electrochemical sensors, molecular
evidence for the importance of secondary bonds in the molecular
recognition, liquid crystals, catalysis or even nanoparticles.4–15
architecture; in many of the complexes hydrogen bonding is
1,1ꢀ-Symmetrically substituted ferrocene species with several O,
present.
N, S or P donor centres are well-known, but species bearing
different substituents in the cyclopentadienyl rings are much
less common. Unsymmetrical ligands are important in view
of their hemilability for catalysis.16 The first report of a P,S
Results and discussion
asymmetrically substituted ferrocene was made by Liu et al.
The ligand 1-diphenylphosphino-1ꢀ-(phenylsulfanyl)ferrocene,
Fc(SPh)PPh2, has been synthesized by reaction of FcLi2·TMDA
with ClSnBu3 and subsequent reactions with ClPPh2 and Ph2S2.
We have prepared the ligands Fc(SPh)PPh2 and Fc(SePh)PPh2
according to the published method described for the related
ligand Fc(SMe)PPh2.23 The reaction of FcLi2(TMDA) with
Cl2PPh leads to the 1,1ꢀ-diphenylphosphinoferrocenophane
ligand (FcPPh). This phosphine was then treated with PhLi
to cleave one of the P–C bonds and give the 1-lithio-1-
diphenylphosphinoferrocene, which reacts in situ with S2Ph2
or Se2Ph2 to afford the unsymmetrical derivatives (Scheme 1).
Compound 2 is an air- and moisture-stable orange solid. The 1H
NMR spectrum shows four different resonances for the a and
b protons of each cyclopentadienyl ring and the 31P(1H) NMR
spectrum one resonance at −17.0 ppm, indicating the presence
of a free phosphine ligand.
who described the synthesis of the Fc(SPh)(PPh2) derivative
via selective transmetallation reactions of Fc(SnBu3)2, although
no metal complexes were reported.17,18 An alternative five-
step synthesis was reported by Dong et al.19 The compound
FcBr2 was used as starting material to prepare the trisub-
stituted species [Fe{1,2-(PPh2)(SMe)(g -C5H3)}{(1ꢀ-(SMe)(g -
C5H4)]20 and a chiral phosphine-thioether ferrocene ligand has
been used in the asymmetric addition of diethylzinc to alkylidine
malonates.21 Also the reaction of aldehydes with isocyanoacetate
has been reported by Hayashi et al. to be catalysed by a chiral
ferrocenylphosphine–gold(I) complex.22 Long et al. have devel-
oped a new synthesis of several unsymmetrical P,S derivatives of
the type Fc(SR)(PPh2) (R = H, Me, Mes), involving the reaction
of FcLi2(TMDA) with a mixture of ClPPh2 and R2S2. The
coordination chemistry of these ligands towards several metals
such as nickel, palladium or rhodium has been studied.23–25
5
5
T h i s j o u r n a l i s
T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 5
D a l t o n T r a n s . , 2 0 0 5 , 3 0 0 5 – 3 0 1 5
3 0 0 5
©

View Article Online
Scheme 1 (i) Cl2PPh, (ii) LiPh (iii) S2Ph2 or Se2Ph2.
Synthesis of gold complexes
The reaction of the ligands 1 or 2 with [Au(tht)2]ClO4
in a molar ratio 2 : 1 leads to the homoleptic complexes
[M{Fc(EPh)PPh2}2]ClO4 (E = S(7), Se (8)). Complexes 7 and 8
are air- and moisture-stable yellow (7) or orange (8) solids that
The reaction of Fc(EPh)PPh2 with [AuX(tht)] (tht = tetrahy-
drothiophene) gives the complexes [AuX{Fc(EPh)PPh2}] (E =
S, X = Cl (3), C6F5 (4)), (E = Se, X = Cl (5), C6F5 (6)) in
good yield (see Scheme 2). The compounds are yellow–orange
air- and moisture-stable solids that behave as non-conductors
in acetone solutions. The IR spectra for complexes 3 and 5
show the absorptions arising from the vibrations t(Au–Cl) at
336 (m) and 335 (m) cm−1, respectively. For complexes 4 and 6
the typical absorptions of a pentafluorophenyl unit bonded to
gold(I) appear around 1500 (vs), 954 (s) and 800 (m) cm−1. In
1
behave as 1 : 1 electrolytes in acetone solutions. The H NMR
spectra show the presence of four multiplets or two multiplets
for the cyclopentadienyl protons. In the 31P NMR spectra one
resonance at 40.1 and 37.5 ppm, respectively, appears for the
equivalent phosphorus atoms. In the mass spectra the cation
molecular peaks at m/z = 1153 (7, 53%) and 1247 (8, 35%)
can be observed. The reaction of 1 with [Au(tht)2]ClO4 in a
molar ratio 1 : 1 was also carried out and gives a compound of
stoichiometry [Au2{Fc(SPh)PPh2}2](ClO4)2 (9). In the 31P NMR
spectrum two different phosphorus environments are observed,
one signal at 27.6 and other at 38.3 ppm; this could indicate the
presence of two different isomers of complex 9, one would be the
“head to head” and the other “head to tail” (Fig. 1). This would
1
the H NMR spectra four resonances for the cyclopentadienyl
protons are not observed because some of them are overlapped;
thus for complexes 3, 4 and 6 three signals with a ratio 1 :
1 : 2 can be observed whereas for 5 only a broad resonance
appears. The 31P NMR spectra indicate that the coordination of
the gold(I) atoms takes place via phosphorus because a low-field
displacement is observed; the position is very similar for the
sulfur or the selenium derivatives, 28.1 (3) and 27.1 (5) ppm, or
37.7 (4), 38.1 (6) ppm. The 19F NMR spectra for 4 and 6 show
the typical pattern for a pentafluorophenyl group with three
resonances corresponding to the ortho, meta and para fluorine
atoms. In the liquid secondary-ion mass spectra the molecular
peaks appear at m/z = 710 (3, 70%), 842 (4, 100%), 882 (6, 25%);
for compound 5 only the fragment arising from the loss of the
chloro ligand at m/z = 723 (30%) can be observed.
Fig. 1 The two possible isomers of complex 9.
Scheme 2 (i) [AuCl(tht)] or [Au(C6F5)(tht)], (ii) 1/2 [Au(tht)2]ClO4, (iii) [Au(tht)2]ClO4, (iv) [Au(OTf)(PPh3)], (v) [Au(C6F5)3(tht)], (vi) 2 [Au(C6F5)3-
(OEt2)], (vii) [Au(C6F5)2(OEt2)2]ClO4.
3 0 0 6
D a l t o n T r a n s . , 2 0 0 5 , 3 0 0 5 – 3 0 1 5

View Article Online
also explain the different chemical shifts, the signal at 27.6 is
in the typical region for a P–Au–S unit and that at 38.3 for a
P–Au–P unit. The 1H NMR spectrum is also in agreement with
the presence of the two isomers.
overlapped. In the LSIMS+ the molecular peaks appear at
m/z = 1176 (11, 34%), 1224 (12, 10%). For complex 13, which
has two Au(C6F5)3 units, the molecular peak is not present but
the fragment arising from the loss of two pentafluorophenyl units
appears at m/z = 1580 (13, 30%).
The treatment of 1 with [Au(OTf)(PPh3)] gives the mixed
phosphine complex [Au(PPh3){Fc(SPh)PPh2}]OTf (10). As hap-
pens with other asymmetric gold(I) complexes, this deriva-
tive is in equilibria in solution with the homoleptic species,
[Au(PPh3)2]OTf and [Au{Fc(SPh)PPh2}2]OTf, although the
equilibria are strongly displaced in the direction of the het-
eroleptic compound. This can be easily seen in the 31P(1H)
NMR spectrum where complex 10 presents an AB system for the
two different phosphorus, whereas the homoleptic species show
only one signal for the equivalent phosphorus atoms. In the
1H NMR spectrum compound 10 (most abundant) shows four
resonances for the cyclopentadienyl protons. In the mass spectra
all the fragments corresponding to all these cationic peaks are
present, at m/z = 937 (9, 25%), 721 ([Au(PPh3)2]+, 20%), 1153
([Au{Fc(SPh)PPh2}2]+, 10%).
The complex [Au(C6F5)2{Fc(SePh)PPh2}]ClO4 (14) has been
prepared by reaction of 2 with [Au(C6F5)2(OEt2)2]ClO4. In this
complex we suppose that the gold(III) centre is coordinated to
the phosphorus and selenium atoms of the heterodifunctional
ligand. Complex 14 is an orange–red air- and moisture-stable
solid that behaves as a 1 : 1 electrolyte in acetone solution. In
the IR spectrum the absorptions from the pentafluorophenyl
groups and the perchlorate anion appear at 1100 (s, br) and
1
619 (m) cm−1, respectively. In the H NMR spectrum all the
protons of the cyclopentadienyl rings are inequivalent and
appear as seven multiplets because two of them are overlapped.
The 31P(1H) NMR spectrum shows only one resonance at
33.4 ppm for the phosphorus atom. In the 19F NMR spectrum
six resonances for the two different pentafluorophenyl units can
be observed. The LSIMS+ spectrum shows the cation molecular
peak at m/z = 944 (20%).
Gold(III) derivatives of the type [Au(C6F5)3{Fc(EPh)PPh2}]
(E = S (11), Se (12)) or [Au2(C6F5)6{Fc(EPh)PPh2}] (E =
Se (13)) have been obtained by reaction of the ligands with
[Au(C6F5)3(OEt2)] in 1 : 1 and 1 : 2 molar ratio. Complexes
11–13 are yellow (11) or orange (12, 13) air- and moisture-
stable solids that behave as non-conductors in acetone solution.
The IR spectra show the typical absorptions arising from a
tris(pentafluorophenyl)gold fragment around 970 (s), 803 (s)
Synthesis of silver and copper complexes
The reaction of 1 or 2 with AgOTf in a molar ratio 1 : 1 gives the
complexes with stoichiometry [Ag(OTf){Fc(EPh)PPh2}] (E = S
(15), Se (16)) (see Scheme 3). Complexes 15 and 16 are yellow or
orange, respectively, air- and moisture-stable solids that are non-
conductors in acetone solutions, which means that the triflate is
coordinated to the silver centre. In the IR spectra the absorptions
for a covalent trifluoromethanesulfonate anion are observed and
appear around tas(SO3) = 1320 (vs) and 1307 (vs), tsym(CF3) =
1229 (m), tasym(CF3) = 1199 (vs) and tsym(SO3) = 1098 (vs) cm−1.
In the 1H NMR the signals for the cyclopentadienyl rings again
appear overlapped and only three multiplets in a ratio 2 : 2 :
4 for compound 15 and two multiplets in a 4 : 4 ratio for
complex 16 can be observed. Only one resonance appears in
the 31P(1H) NMR spectra, in agreement with the presence of
only ◦one type of phosphorus atom at room temperature. At
−55 C two doublets appear because of the coupling with the
1
and 795 (s) cm−1. In the H NMR spectra the protons of the
cyclopentadienyl rings appear as several multiplets. Although
all of them should be inequivalent, the rapid exchange means
that sometimes the resonances are overlapped; we thus observed
4 (11), 3 (12), or 5 (13) resonances with different integral ratios.
Only one signal is observed in the 31P(1H) NMR spectra for these
complexes, as expected for one type of phosphorus atom. The
19F NMR spectra of complexes 11 and 12 shows the presence of
two different pentafluorophenyl groups in the ratio 2 : 1, each
group showing three resonances for the ortho, meta and para
fluorine atoms, respectively. For compound 13 four different
types of pentafluorophenyl units should appear, corresponding
to twelve different resonances, but some of the positions are
Scheme 3 (i) [Ag(OTf)], (ii) 1/2 [Ag(OTf)], (iii) [Ag(OTf)(PPh3)] (iv) [Cu(NCMe)4]PF6.
D a l t o n T r a n s . , 2 0 0 5 , 3 0 0 5 – 3 0 1 5
3 0 0 7

View Article Online
two silver nuclei, 107Ag and 109Ag. In the mass spectra, the
cation molecular peaks appear at m/z = 585 (15, 100%) and
633 (16, 100%).
result is a mixture of complexes from which we have identified
[Au(C6F5)(PPh3)], [Au{Fc(SPh)PPh2}2]+ (7) and starting mate-
rial. Also the treatment of [Au(PPh3){Fc(SPh)PPh2}]OTf (10)
with [Ag(OTf)(PPh3)] gives complex 19 and [Au(PPh3)2]OTf.
Therefore, all the reactions aimed at preparing mixed gold–silver
complexes have led to a mixture of complexes in which both the
homoleptic and heteroleptic species exist. Only in one case could
we obtain a pure product and this came from the reaction of
[AuCl{Fc(SePh)PPh2}] (5) with [PdCl2(NCPh)2] in a molar ratio
of 2 : 1 from which the complex [{AuCl{Fc(SePh)PPh2}}2PdCl2]
(23) could be isolated. Complex 23 is an air- and moisture-stable
The reaction of 1 with AgOTf in a molar ratio 2 : 1 gives the
complex [Ag{Fc(SPh)PPh2}2]OTf (17), which is a yellow air- and
moisture-stable solid that behaves as a 1 : 1 electrolyte in acetone
solutions. In the IR spectrum the trifluoromethanesulfonate
is only acting as the counterion, as can be seen from the
absorptions at tasym(SO3) = 1272 (vs), tsym(CF3) = 1237 (m),
tasym(CF3) = 1156 (vs) and tsym(SO3) = 1025 (vs) cm−1. The
1H NMR spectrum presents, apart from the multiplet due to
the phenyl protons, four multiplets for the cyclopentadienyl
protons. The 31P(1H) NMR spectrum shows a broad singlet
at room temperature that splits into two doublets at −55 ◦C
because of the coupling with the silver nuclei. In the LSIMS+
the cation molecular peak appears at m/z = 1065 (10%)
and also the fragment at m/z = 585 (50%) corresponding to
[Ag{Fc(SPh)PPh2}]+ is present.
1
red solid that is a non-conductor in acetone solutions. The H
NMR spectrum shows three multiplets in a ratio 2 : 3 : 3 for
the cyclopentadienyl protons and the 31P(1H) spectrum presents
only one peak at 28.3 ppm for the two equivalent phosphorus
atoms.
The treatment of
1 or 2 with [Ag(OTf)(PPh3)] in
dichloromethane leads to the four-coordinated derivatives
[Ag(OTf)(PPh3){Fc(EPh)PPh2}] (E = S (18), Se (19)). Com-
plexes 18 and 19 are yellow or orange, respectively, air- and
moisture-stable solids. Their conductivities in acetone solutions
are 10.1 and 15 X−1 cm2 mol−1, which means that the triflate
ligand may dissociate to some extent. In the IR spectra the bands
(1)
1
for a covalent triflate anion can be observed. In the H NMR
spectra three resonances for complex 18 and four resonances
for compound 19 are associated with the cyclopentadienyl
protons. The 31P(1H) NMR spectra show broad signals at room
temperature; at low temperature eight doublets are observed
as a consequence of the presence of an AB system coupled
to the two silver nuclei. In the mass spectra (LSIMS+) the
cations molecular peaks appear at m/z = 847 (18, 15%) and 895
(19, 30%).
(2)
Electrochemistry
The reaction of 1 or 2 with the copper compound
[Cu(NCMe)4]PF6 in a molar ratio 1 : 1 has also been carried out
and gives the derivative [Cu{Fc(EPh)PPh2}2]PF6 (E = S (20), Se
(21)). In the same manner as for silver(I), and because of the high
tendency of copper to adopt higher coordination numbers than
gold(I), we propose a tetrahedral geometry for complexes 20 or
21. These compounds are yellow or orange solids that behave as
The electrochemical behaviour of some gold or silver complexes
with the ligand Fc(SPh)PPh2 have been studied by cyclic
voltammetry at a platinum electrode in CH2Cl2. The free
ligand undergoes a reversible one-electron oxidation process,
based on the ferrocene unit, very close to that of ferrocene,
0.53 V. With respect to the ligand, the gold or silver complexes
undergo anodic oxidations at higher potentials, as we have
observed for other metal complexes. For example the complex
[Au(C6F5){Fc(SPh)PPh2}] has a reversible oxidation process at
0.84 V. The silver complexes present a more complicated pattern
because of the presence of one or two silver(I) atoms that can be
oxidized to Ag2+. Then the complex [Ag(OTf){Fc(SPh)PPh2}]
presents a ferrocene-based reversible oxidation wave at 0.94 V
and irreversible oxidation for the silver at 1.2 V. When a further
ligand is bonded to silver such as triphenylphosphine as in
[Ag(OTf)(PPh3){Fc(SPh)PPh2}] there is an anodic displacement
for the oxidation of the Ag(I) at 1.66 V, whereas the ferrocene–
ferrocenium oxidation has a similar value, 0.91 V.
1
1 : 1 electrolytes in acetone solutions. Their H NMR spectra
show signals from the cyclopentadienyl protons as four multi-
plets in the ratio 1 : 5 : 1 : 1 for complex 20 and four multiplets
in a ratio 2 : 2 : 2 : 2 for 21. In the 31P(1H) NMR spectra only
one resonance appears for the equivalent phosphorus atoms, at
−8.9 and −7.6 ppm, respectively.
Synthesis of heteropolynuclear complexes
In the above-mentioned gold(I) complexes, it is noticeable that
coordination, with the exception of 9, takes place only through
the phosphorus atom. We therefore considered it interesting
to study further coordination of some of these complexes
to other metal centres in order to obtain heteropolynuclear
derivatives. In this manner we attempted the reaction of [Au{Fc-
(SPh)PPh2}2]ClO4 with AgClO4, which gives the compound
[AuAg{Fc(SPh)PPh2}2](ClO4)2 (22) in which the silver atom will
be bonded to the sulfur centres. In the 31P(1H) NMR spectrum
one strong resonance at 39 ppm is observed and assigned to
complex 22 and a weaker resonance at 30.1 also appears. We
think that this signal could be attributable to some isomerization
process to give the P–Au–S/P–Ag–S isomer (eqn. (2)), although
the signal for the phosphorus atom bonded to silver is not
observed, probably because of the small amount of this isomer
and because Ag–P bonds usually give broad signals. We have
tried other reactions of gold complexes with other silver salts,
for example the reaction of [Au(C6F5){Fc(SPh)PPh2}] (4) with
[Ag(OTf)(PPh3)] with the idea that the silver atom will coordi-
nate to the free sulfur donor atom in the starting compound. The
Crystal structures
The crystal structures of complexes [AuCl{Fc(EPh)PPh2}] (E =
S (3), Se (5)) have been established by X-ray diffraction studies
(Fig. 2 and 3). Selected bond lengths and angles are shown in
Tables 1 and 2, respectively. It is noteworthy that the compounds
◦
˚
Table 1 Selected bond lengths [A] and angles [ ] for complex 3
Au–P
2.2280(9)
2.2939(10)
1.796(4)
P–C(21)
S–C(36)
S–C(41)
1.827(4)
1.753(4)
1.767(4)
Au–Cl
P–C(31)
P–C(11)
1.813(4)
P–Au–Cl
176.67(4)
108.31(16)
106.64(17)
104.69(17)
C(31)–P–Au
C(11)–P–Au
C(21)–P–Au
C(36)–S–C(41)
110.18(12)
116.94(13)
109.50(12)
102.67(18)
C(31)–P–C(11)
C(31)–P–C(21)
C(11)–P–C(21)
3 0 0 8
D a l t o n T r a n s . , 2 0 0 5 , 3 0 0 5 – 3 0 1 5

View Article Online
◦
˚
Table 2 Selected bond lengths [A] and angles [ ] for complex 5
Au–P
2.2220(15)
2.2847(16)
1.778(6)
P–C(21)
Se–C(1)
Se–C(11)
1.823(6)
1.893(7)
1.931(6)
Au–Cl
P–C(6)
P–C(31)
1.813(6)
P–Au–Cl
176.81(6)
106.5(3)
104.1(3)
104.1(3)
C(6)–P–Au
112.1(2)
114.7(2)
114.3(2)
98.0(3)
C(6)–P–C(31)
C(6)–P–C(21)
C(31)–P–C(21)
C(31)–P–Au
C(21)–P–Au
C(1)–Se–C(11)
Fig. 4 One-dimensional chain formed through Au · · · Cl and Au · · · Se
interactions in complex 5.
˚
from 2.7 to 2.9 A and are mostly of acceptable linearity to be
considered as hydrogen bonds.
The structures of complexes 4 and 6 (which again are not
isostructural; 4 is a hexane solvate) have also been confirmed
by X-ray diffraction studies and are shown in Figs. 5 and
6, with a selection of bond lengths and angles in Tables 3
and 4, respectively. For complex 6 there are two independent
molecules in the asymmetric unit. The gold atoms are again in
Fig. 2 The structure of complex 3 in the crystal with the atom
numbering scheme. Radii are arbitrary. The H atoms are omitted for
clarity.
Fig. 3 Structure of complex 5. The H atoms are omitted for clarity.
Fig. 5 Perspective view of complex 4. The H atoms are omitted for
clarity.
are not isostructural, although neither compound is a solvate
(cf. other homologous pairs below) and both have equivalent
molecular structures. The reason could be the differences in
the positions of the substituents in the Cp rings: for the
sulfur derivative the cyclopentadienyl rings are almost eclipsed
(torsion angle about the ring centroid 3.2◦) with an angle
between both substituents of approximately 72◦, whereas for
the selenium compound the cyclopentadienyl rings are also
practically eclipsed (torsion angle about the ring centroid 5.5◦)
but the angle between both substituents is approximately 144◦.
In both complexes the gold atoms display the expected linear
geometry with P–Au–Cl angles of 176.67(4) and 176.81(6)◦.
The Au–P and Au–Cl bond distances are very similar in both
˚
complexes, 2.2280(9), 2.2220(16) and 2.2939(10), 2.2847(16) A
and are typical for Cl–Au–P derivatives. There are no short
intermolecular Au–Au contacts; the shortest are around 4.8 A.
˚
Fig. 6 The structure of complex 6 in the crystal, showing the two
independent molecules.
In complex 5 there are intramolecular Au · · · Cl and Au · · · Se
˚
contacts around 3.7 A that lead to the formation of a chain
◦
˚
Table 3 Selected bond lengths [A] and angles [ ] for complex 4
structure (Fig. 4).
The gold atoms are located relatively close to one C–C bond of
the cyclopentadienyl group, the distances are 3.309 and 3.498 A
Au–C(11)
Au–P
P–C(1)
P–C(31)
2.056(6)
2.2701(16)
1.800(6)
1.811(6)
P–C(41)
S–C(10)
S–C(21)
1.814(6)
1.761(6)
1.782(6)
˚
for the sulfur (to C31 and C32, respectively) and 3.327 and
˚
3.623 A for the selenium derivative (to C6 and C7, respectively).
2
This could indicate the presence of a weak g interaction with
C(11)–Au–P
177.13(17)
105.3(3)
103.6(3)
103.7(3)
C(1)–P–Au
114.84(19)
115.33(19)
112.7(2)
the Cp ring, as we have observed in other gold or silver
complexes with ferrocene moieties.27,28 In the lattice there are
several Cl · · · H or Au · · · H interactions involving the protons
of the phenyl and cyclopentadienyl groups. These contacts range
C(1)–P–C(31)
C(1)–P–C(41)
C(31)–P–C(41)
C(31)–P–Au
C(41)–P–Au
C(10)–S–C(21)
101.8(3)
D a l t o n T r a n s . , 2 0 0 5 , 3 0 0 5 – 3 0 1 5
3 0 0 9

View Article Online
◦
◦
˚
˚
Table 5 Selected bond lengths [A] and angles [ ] for complex 15
Table 4 Selected bond lengths [A] and angles [ ] for complex 6
Au(1)–C(21)
Au(1)–P(1)
Se(1)–C(1)
Se(1)–C(11)
P(1)–C(6)
P(1)–C(41)
P(1)–C(31)
2.049(5)
2.2773(14) Au(2)–P(2)
1.896(7)
1.935(6)
1.797(6)
1.808(6)
1.813(6)
Au(2)–C(71)
2.037(5)
2.2643(15)
1.881(6)
1.913(6)
1.792(6)
1.807(5)
1.808(6)
Ag–O(1)a
Ag–O(1)
Ag–S(1)
P–C(46)
P–C(31)
P–C(21)
S(1)–C(41)
S(1)–C(11)
Ag–P
2.4055(15)
2.4172(15)
2.7123(6)
1.801(2)
1.819(2)
1.821(2)
1.767(2)
1.787(2)
2.3875(6)
Agꢀ–O(1ꢀ)
Agꢀ–O(1ꢀ)b
Agꢀ–S(1ꢀ)
Pꢀ–C(146)
Pꢀ–C(121)
Pꢀ–C(131)
S(1ꢀ)–C(141)
S(1ꢀ)–C(111)
Agꢀ–Pꢀ
2.3905(18)
2.4618(18)
2.7051(6)
1.807(2)
1.823(2)
1.828(2)
1.755(2)
1.780(2)
2.3798(7)
Se(2)–C(51)
Se(2)–C(61)
P(2)–C(56)
P(2)–C(81)
P(2)–C(91)
C(21)–Au(1)–P(1)
C(1)–Se(1)–C(11)
C(6)–P(1)–Au(1)
C(41)–P(1)–Au(1)
C(31)–P(1)–Au(1)
C(5)–C(1)–Se(1)
C(2)–C(1)–Se(1)
Se(1)–C(1)–Fe(1)
P(1)–C(6)–Fe(1)
C(12)–C(11)–Se(1)
C(16)–C(11)–Se(1)
171.17(16) C(22)–C(21)–Au(1) 120.7(4)
98.7(3) C(26)–C(21)–Au(1) 125.8(4)
112.93(18) C(71)–Au(2)–P(2)
117.99(19) C(51)–Se(2)–C(61)
109.40(18) C(56)–P(2)–Au(2)
126.7(5)
125.3(5)
124.6(3)
127.6(3)
116.6(5)
123.6(5)
178.62(16)
99.8(3)
111.82(19)
113.0(2)
115.4(2)
123.6(5)
116.4(5)
P–Ag–O(1)a
138.60(4)
134.71(4)
74.92(6)
108.80(2)
88.95(5)
Pꢀ-Agꢀ–O(1ꢀ)
140.65(4)
130.38(5)
78.82(6)
108.83(2)
92.61(5)
P–Ag–O(1)
Pꢀ–Agꢀ–O(1ꢀ)b
O(1)a–Ag–O(1)
P–Ag–S(1)
O(1ꢀ)–Agꢀ–O(1ꢀ)b
Pꢀ–Agꢀ–S(1ꢀ)
C(81)–P(2)–Au(2)
C(91)–P(2)–Au(2)
C(66)–C(61)–Se(2)
C(62)–C(61)–Se(2)
C(76)–C(71)–Au(2) 121.6(4)
C(72)–C(71)–Au(2) 122.8(4)
O(1)a–Ag–S(1)
O(1)–Ag–S(1)
C(46)–P–Ag
C(31)–P–Ag
C(21)–P–Ag
C(41)–S(1)–Ag
C(11)–S(1)–Ag
S(2)–O(1)–Aga
S(2)–O(1)–Ag
Aga–O(1)–Ag
O(1ꢀ)–Agꢀ–S(1ꢀ)
O(1ꢀ)a-Agꢀ–S(1ꢀ)
C(146)–Pꢀ–Agꢀ
C(121)–Pꢀ–Agꢀ
C(131)–Pꢀ–Agꢀ
C(141)–S(1ꢀ)–Agꢀ
C(111)–S(1ꢀ)–Agꢀ
S(2ꢀ)–O(1ꢀ)–Agꢀ
S(2ꢀ)–O(1ꢀ)–Agꢀa
Agꢀb–O(1ꢀ)–Agꢀ
98.82(5)
92.86(5)
110.42(7)
117.02(7)
114.07(8)
101.43(8)
119.83(8)
122.88(9)
124.12(9)
105.08(6)
110.25(8)
115.74(8)
116.63(8)
99.66(8)
116.03(8)
135.99(11)
110.10(10)
101.18(6)
a linear geometry with C–Au–P angles of 177.13(17)◦ for the
sulfur and 171.17(16)◦ (somewhat distorted) and 178.62(16)◦
for the selenium derivative. The Au–C bond distances are
2.056(6), 2.049(5) and 2.037(5) A, respectively, and are typical
for pentafluorophenyl(phosphine) gold(I) complexes. The Au–
˚
Symmetry transformations used to generate equivalent atoms.a −x + 1,
−y + 1, −z. b −x + 2, −y, −z + 1.
˚
P bond lengths of 2.2701(16), 2.2773(14) and 2.2643(15) A
are longer than those corresponding to the chloro derivatives,
indicating the higher trans influence of the pentafluorophenyl
group. In the selenium derivative there is one intermolecular
◦
˚
Table 6 Selected bond lengths [A] and angles [ ] for complex 16
Ag–O(3)a
Ag–Pb
Ag–O(1)
Ag–Se
2.414(4)
2.4264(17)
2.558(4)
2.6562(8)
1.902(6)
Se–C(11)
P–C(6)
P–C(31)
P–C(21)
1.945(6)
1.806(6)
1.815(6)
1.830(6)
˚
short Au–Se contact of 3.643 A (Fig. 7); this contact is only
present for one of the molecules. The cyclopentadienyl rings
also display an almost eclipsed geometry in both complexes and
the substituents subtend an angle of approximately 144◦. In the
lattice of both complexes there are several secondary bonds of
Se–C(1)
O(3)a–Ag–Pb
O(3)a–Ag–O(1)
Pb–Ag–O(1)
O(3)a–Ag–Se
Pb–Ag–Se
118.21(11)
81.11(13)
115.38(10)
105.14(10)
127.11(5)
99.21(9)
100.5(3)
110.48(17)
99.3(2)
C(21)–P–Agb
C(5)–C(1)–Se
C(2)–C(1)–Se
C(10)–C(6)–P
C(7)–C(6)–P
116.72(19)
128.2(4)
123.9(5)
123.8(5)
130.0(4)
119.9(5)
120.5(5)
118.5(4)
122.6(5)
117.7(5)
123.1(5)
115.9(2)
133.1(2)
˚
˚
the type F · · · H (2.4–2.7 A) and Au · · · H (2.8–2.9 A).
O(1)–Ag–Se
C(1)–Se–C(11)
C(1)–Se–Ag
C(11)–Se–Ag
C(6)–P–C(31)
C(6)–P–C(21)
C(31)–P–C(21)
C(6)–P–Agb
C(16)–C(11)–Se
C(12)–C(11)–Se
C(26)–C(21)–P
C(22)–C(21)–P
C(32)–C(31)–P
C(36)–C(31)–P
S–O(1)–Ag
107.9(3)
100.7(3)
105.5(3)
112.7(2)
112.4(2)
S–O(3)–Aga
C(31)–P–Agb
Symmetry transformations used to generate equivalent atoms.a −x,
−y + 1, −z + 2 b −x + 1, −y + 1, −z + 2.
Fig. 7 Perspective view of the Au–Se interaction for one of the
independent molecules of complex 6.
The structures of compounds 15 and 16 have been established
by X-ray diffraction methods (Figs. 8 and 9, respectively). A
selection of bond lengths and angles are shown in Tables 5 and 6,
respectively. Yet again, the homologous pair is not isostructural.
The structures of these complexes are indeed fundamentally
different. First, complex 15 has a dimeric structure with a
chelating heterodifunctional ligand and the triflate groups as
bridging ligands, whereas compound 16 (for detailed discus-
sion see below) consists of dimeric silver units with bridging
heterodifunctional ligands that are further bonded to other
dimeric units through bridging triflate ligands, thus leading
to a chain structure. Secondly, complex 15 crystallizes as a
dichloromethane solvate (ratio 15 : CH2Cl2 = 1/4).
Fig. 8 Structure of complex 15; one crystallographically independent
dimer.
in both the overall bonding scheme is very similar (except for the
orientation of the triflate ions, with Ag–O–S–C 142 or −98◦) and
consequently we will only discuss one of the molecules. The silver
Complex 15 crystallizes with two independent monomeric
formula units, which associate to dimers by inversion symmetry;
3 0 1 0
D a l t o n T r a n s . , 2 0 0 5 , 3 0 0 5 – 3 0 1 5

View Article Online
◦
˚
Table 7 Selected bond lengths [A] and angles [ ] for complex 18
Ag–P(2)
Ag–P(1)
Ag–O(1)
2.4424(6)
2.4656(6)
2.506(2)
Ag–S(1)
S(1)–C(6)
S(1)–C(11)
2.6741(6)
1.761(2)
1.785(2)
P(2)–Ag–P(1)
P(2)–Ag–O(1)
P(1)–Ag–O(1)
P(2)–Ag–S(1)
P(1)–Ag–S(1)
O(1)–Ag–S(1)
C(1)–P(1)–Ag
C(31)–P(1)–Ag
128.09(2)
121.72(6)
86.98(6)
115.760(19)
105.447(18)
89.83(6)
C(21)–P(1)–Ag
C(41)–P(2)–Ag
C(51)–P(2)–Ag
C(61)–P(2)–Ag
C(6)–S(1)–C(11)
C(6)–S(1)–Ag
C(11)–S(1)–Ag
S(2)–O(1)–Ag
116.53(7)
111.23(7)
122.71(7)
107.90(7)
103.43(11)
107.69(7)
106.29(7)
139.15(17)
111.94(7)
114.05(7)
◦
˚
Table 8 Selected bond lengths [A] and angles [ ] for complex 19
Ag(1)–P(2)
Ag(1)–P(1)
Ag(1)–O(1)
2.4141(13)
2.4208(13)
2.541(4)
Ag(1)–Se(1)
Se(1)–C(10)
Se(1)–C(11)
2.8566(7)
1.895(5)
1.922(5)
Fig. 9 Molecular structure of complex 16.
centres display a distorted tetrahedral geometry, being bridged
by the two oxygen atoms of the triflate ligands and chelated by
the heterofunctional P,S ligand. The most regular angle is P–
Ag–S(1) 108.80(2)◦, with the angles O(1)–Ag–O(1)# (#: −x +
1, −y + 1, −z) 74.92(6)◦ and P–Ag–O(1) 134.71(4)◦ furthest
from ideal values.
P(2)–Ag(1)–P(1)
P(2)–Ag(1)–O(1)
P(1)–Ag(1)–O(1)
P(2)–Ag(1)–Se(1)
P(1)–Ag(1)–Se(1)
144.05(5)
112.44(12)
93.66(12)
103.25(4)
107.17(4)
O(1)–Ag(1)–Se(1)
C(10)–Se(1)–C(11)
C(10)–Se(1)–Ag(1)
C(11)–Se(1)–Ag(1)
75.30(10)
100.2(2)
101.19(15)
114.17(15)
˚
The Ag–P distance of 2.3875(6) A is slightly shorter than
those found in other tetra-coordinated silver complexes such
as [Ag(dppe)2]NO3 (dppe = bis(diphenylphosphino)ethane)29
˚
with distances in the range 2.488(3) to 2.527(3) A. The Ag–S
˚
distance, 2.7123(6) A, is considerably longer than those found
in the silver compound [Ag(OTf){Fc(SPh)2}]2 (2.5037(8) and
2.5558(8) A),26e with a similar dimeric structure, and indicates a
˚
weaker bond. The Ag–O distances of 2.4055(15) and 2.4172(15)
˚
A correspond to medium strength bonds.
The structure of complex 16 is a chain polymer consisting of
linked rings. The asymmetric unit corresponds to the fragment
[Ag(OTf){Fc(SePh)PPh2}], which gives rise to a dimer via an
inversion centre, whereby the heterodifunctional ligands bridge
both silver centres. The silver atom is bonded to one oxygen
atom (O1) of the triflate anion within this first dimer, and also
to a further oxygen (O3, generated via a second inversion centre).
The triflates thus act as bridging ligands between silver centres,
leading to eight-membered rings (Ag–O–S–O)2 and finally to the
chain polymer (Fig. 10). The geometry around the silver centre is
again distorted tetrahedral with angles P#2–Ag–Se 127.11(5)◦,
P#2–Ag–O(1) 115.38(10)◦, O(1)–Ag–Se 99.21(9)◦ and O(3)#1-
Ag–O(1) 81.11(13)◦ (#1 –x, −y + 1, −z + 2; #2 − x + 1, −y +
Fig. 11 Perspective view of complex 18 in the crystal.
˚
1, −z + 2). The Ag–Se distance is 2.6562(8) A and is similar
to those found in the complex [Ag(OTf){Fc(SePh)2}] (2.5888(4)
˚
and 2.6339(3) A), which has a dimeric structure with a bridging
triflate ligand.26e The Ag–O distances are somewhat dissimilar,
˚
2.414(4) and 2.558(4) A, indicating a weaker bond to the triflate
group within the asymmetric unit.
Fig. 12 The structure of complex 19 in the crystal.
Fig. 10 Structure of the chain polymer of complex 16.
Both compounds are simple monomers. For complex 18 the
triflate ligand is disordered over two positions, but the second
position is only occupied to the extent of 15%. In both complexes
the geometry around the silver centre is distorted tetrahedral.
We have also established the crystal structure of compounds
18 and 19, which are shown in Figs. 11 and 12, respectively. A se-
lection of bond lengths and angles can be seen in Tables 7 and 8.
D a l t o n T r a n s . , 2 0 0 5 , 3 0 0 5 – 3 0 1 5
3 0 1 1

View Article Online
The most regular angle is the bite angle of the heterofunc-
tional ligand, P(1)–Ag–S(1) 105.447(18)◦ and P(1)–Ag–Se(1)
Perchlorate salts of metal complexes with organic ligands
are potentially explosive. Only small amounts of material
should be prepared, and these should be handled with great
caution.
˚
107.17(4) A and the most irregular corresponds to the P–Ag–P
˚
angles of 128.09(2) and 144.09(4) A, respectively.
˚
The distance Ag–S is 2.6741(6) A and Ag–Se is 2.8595(6)
˚
A, which are rather long compared with other more regularly
tetra-coordinated silver derivatives, indicating only a weak
bond. The cyclopentadienyl rings are almost staggered and the
substituents are located in opposite directions with an angle of
approximately 72◦.
Synthesis
Synthesis of [Fc(EPh)PPh2] (E = S (1), Se (2)). To a solution
of FcPPh2 (0.292 g, 1 mmol) in diethyl ether (20 mL) at 0 ◦C was
added dropwise PhLi (0.55 ml, 1 mmol). After 1 h of reaction,
PhSSPh (0.218 g, 1 mmol) or PhSeSePh (0.312 g, 1 mmol) was
added and the mixture was stirred for 24 h at room temperature.
The solutions were washed with water and the organic phase
dried over Na2SO4. Evaporation of the solvent gave a residue
that was chromatographed over alumina using hexane : diethyl
ether (4 : 1) as eluent. The first band corresponds to compounds 1
or 2, respectively. Compound 1: Yield 56%. Compound 2: Yield:
51%. KM 1.3 X−1 cm2 mol−1. Elemental analysis (%), Found: C,
63.54; H, 4.03. Calc. for C28H23FeO3PSe: C, 64.00; H, 4.38. NMR
Conclusions
The synthesis of the unsymmetrical ligands Fc(EPh)PPh2
(E = S, Se) and coordination studies to group 11 metal
compounds is described. These heterodifunctional ligands
posses two donor atoms P,S or P,Se with different coordi-
nation capabilities. This can be seen in the complexes ob-
tained with the three metals; gold predominantly coordinates
through the phosphorus atom except when a weak ligand
is displaced, as in the reaction with the gold(I) deriva-
tive [Au(tht)2]ClO4 (1 : 1) or with the gold(III) complex
[Au(C6F5)2(OEt2)2]ClO4 to give [Au2{Fc(SPh)PPh2}2](ClO4)2
and [Au(C6F5)2{Fc(SePh)PPh2}]ClO4, respectively. The greater
tendency of silver(I) and copper(I) to give complexes with high
coordination numbers produces complexes with coordination
to both phosphorus and chalcogen atoms. Four pairs of
homologous compounds have been characterized by X-ray
diffraction, but surprisingly not a single pair is isotypic. In many
of the complexes a supramolecular structure is formed through
secondary bonds such as Au · · · H, F · · · H hydrogen bonds and
Au · · · Cl or Au · · · Se interactions.
1
data. H, d: 4.03 (m, 2H, C5H4), 4.14 (m, 2H, C5H4), 4.28 (m,
2H, C5H4), 4.40 (m, 2H, C5H4), 7.06–7.45 (m, 15H, Ph). 31P(1H),
d: −17.0 (s, 1P, PPh2) ppm.
Synthesis of [AuX{Fc(EPh)PPh2}] (E = S, X = Cl (3),
C6F5 (4);), (E = Se, X = Cl (5), C6F5 (6). To a solution of
[Fc(SPh)PPh2] (0.048 g, 0.1 mmol) or [Fc(SePh)PPh2] (0.053 g,
0.1 mmol) in 20 mL of dichloromethane was added to the
corresponding amount of [AuCl(tht)] (0.032 g, 0.1 mmol) or
[Au(C6F5)(tht)] (0.045 g, 0.1 mmol) and the mixture stirred for
15 min. The solution was concentrated to ca. 5 mL and addition
of hexane (10 mL) gave complexes 3, 4, 5 or 6 as yellow–
orange solids. Complex 3: yield 89%. KM 3.1 X−1 cm2 mol−1.
Elemental analysis (%), Found: C, 47.20; H, 3.40; S, 4.68.
Calc. for C28H23AuClFePS: C, 47.31; H, 3.26; S, 4.51. NMR
data. 1H, d: 4.39 (m, 2H, C5H4), 4.45 (m, 4H, C5H4), 4.67
(m, 2H, C5H4), 7.10–7.68 (m, 15H, Ph). 31P(1H), d: 28.1 (s,
1P, PPh2) ppm. Complex 4: yield 87%. KM 1.5 X−1 cm2 mol−1.
Elemental analysis (%), Found: C, 48.84; H, 2.75; S, 3.95. Calc.
for C34H23AuF5FePS: C, 48.47; H, 2.75; S, 3.80. NMR data.
1H, d: 4.46 (m, 4H, C5H4), 4.54 (m, 2H, C5H4), 4.65 (m, 2H,
C5H4), 6.95–7.77 (m, 15H, Ph). 31P(1H), d: 37.7 (s, 1P, PPh2)
Although the gold(I) complexes are suitable precursors for the
synthesis of heteropolynuclear compounds, the reaction with
other metallic centers occurs but in most of the cases leads
to a mixture of compounds, with the exception of the gold–
silver derivative [AuAg{Fc(SPh)PPh2}2](ClO4)2 or the gold–
palladium species complex [{AuCl{Fc(SePh)PPh2}}2PdCl2].
Experimental
3
ppm. 19F, d: −116.4 (m, 2F, o-F), −158.8 (t, 1F, p-F, J(FF)
Instrumentation
19.6 Hz), −162.6 (m, 2F, m-F). Complex 5: yield 89%. KM 3.8
X−1 cm2 mol−1. Elemental analysis (%), Found: C, 43.96; H, 3.03.
Calc. for C28H23AuClFePSe: C, 44.38; H, 3.05. NMR data. 1H,
d: 4.03 (m, 8H, C5H4), 7.05–7.58 (m, 15H, Ph). 31P(1H), d: 27.2
(s, 1P, PPh2) ppm. Complex 6: yield 68%. KM 0.8 X−1 cm2 mol−1.
Elemental analysis (%), Found: C, 45.51; H, 2.50. Calc. for
Infrared spectra were recorded in the range 4000–200 cm−1 on a
Perkin-Elmer 883 spectrophotometer using Nujol mulls between
polyethylene sheets. Conductivities were measured in ca. 5 ×
10−4 mol dm−3 solutions with a Philips 9509 conductimeter.
C, H and S analyses were carried out with a Perkin-Elmer
2400 microanalyzer. Mass spectra were recorded on a VG
Autospec, with the liquid secondary-ion mass spectra (LSIMS)
technique, using nitrobenzyl alcohol as matrix. NMR spectra
were recorded on a Varian Unity 300 spectrometer, a Bruker
ARX 300 spectrometer in CDCl3 (otherwise stated). Chemical
shifts are cited relative to SiMe4 (1H, external), 85% H3PO4
(31P, external) and CFCl3 (19F, external). Cyclic voltammetric
experiments were performed employing an EG & PARC model
273 potentiostat. A three-electrode system was used, which
consists of a platinum disk working electrode. The measurements
were carried out in CH2Cl2 solutions with 0.1 mol dm−3 Bu4NPF6
as a supporting electrolyte. Under the present experimental
conditions, the ferrocenium–ferrocene couple was located at
0.47 V vs. SCE.
1
C34H23AuF5FePSe: C, 45.92; H, 2.60. NMR data. H, d: 4.38
(m, 4H, C5H4), 4.43 (m, 2H, C5H4), 4.56 (m, 2H, C5H4), 7.08–
7.62 (m, 15H, Ph). 31P(1H), d: 27.2 (s, 1P, PPh2) ppm. 19F, d:
3
−117.0 (m, 2F, o-F), −159.5 (t, 1F, p-F, J(FF) 20 Hz, −163.4
(m, 2F, m-F).
Synthesis of [Au{Fc(EPh)PPh2}2]ClO4 (E = S (7), Se(8)).
To
a solution of [Fc(SPh)PPh2] (0.096 g, 0.2 mmol)
or [Fc(SePh)PPh2] (0.106 g, 0.2 mmol) in 20 mL of
dichloromethane was added [Au(tht)2]ClO4 (0.047 g, 0.1 mmol)
and the mixture stirred for 15 min. Concentration of the solution
to ca. 5 mL and addition of diethyl ether (10 mL) gave complexes
7 or 8 as yellow or orange solids, respectively. Complex 7: yield
80%. KM 101.4 X−1 cm2 mol−1. Elemental analysis (%), Found: C,
53.48; H, 3.54; S, 4.95. Calc. for C56H46AuClFe2O4P2S2: C, 53.67;
Materials
1
H, 3.70; S, 5.11. NMR data. H, d: 4.23 (m, 2H, C5H4), 4.36
The starting materials FcPPh,30 [AuCl(tht)],31 [Au(C6F5)(tht)],31
[Au(tht)2]ClO4,32 [Au(C6F5)3(OEt2)],33 [Au(C6F5)2(OEt2)2]ClO4,33
[Ag(OTf)(PPh3)]34 and [PdCl2(NCPh)2]35 were prepared by
published procedures. [Au(OTf)(PPh3)] was prepared from
[AuCl(PPh3)]36 by reaction with AgOTf in dichloromethane.
(m, 2H, C5H4), 4.47 (m, 2H, C5H4), 5.79 (m, 2H, C5H4), 6.65–
7.81 (m, 30H, Ph). 31P(1H), d: 40.1 (s, 2P, PPh2) ppm. Complex
8: yield 82%. KM 97.1 X−1 cm2 mol−1. Elemental analysis (%),
Found: C, 49.49; H, 3.63. Calc. for C56H46AuClFe2O4P2Se2: C,
1
49.93; H, 3.44. NMR data. H, d: 4.84 (m, 8H, C5H4), 5.12
3 0 1 2
D a l t o n T r a n s . , 2 0 0 5 , 3 0 0 5 – 3 0 1 5

View Article Online
(m, 8H, C5H4), 6.71–7.58 (m, 30H, Ph). 31P(1H), d: 37.5 (s, 2P,
PPh2) ppm.
solution to ca. 5 mL and addition of hexane (10 mL) gave
complex 14 as an orange solid. Yield 62%. KM 136 X−1 cm2 mol−1.
Elemental analysis (%), Found: C, 41.90; H, 2.15. Calc. for
Synthesis of [Au2{Fc(SPh)PPh2}2](ClO4)2 (9). To a solu-
tion of [Fc(SPh)PPh2] (0.096 g, 0.2 mmol) in 20 mL of
dichloromethane was added [Au(tht)2]ClO4 (0.094 g, 0.2 mmol)
and the mixture was stirred for 15 min. Concentration of the
solution to ca. 5 mL and addition of diethyl ether (10 mL) gave
complex 9 as a yellow solid. Yield 76%. KM 187.2 X−1 cm2 mol−1.
Elemental analysis (%), Found: C, 43.65; H, 3.05; S, 4.34. Calc.
for C56H46Au2Cl2Fe2O8P2S2: C, 43.40; H, 2.99; S, 4.13. NMR
1
C40H23AuClF10FeO4PSe: C, 41.56; H, 2.00. NMR data. H, d:
4.63 (m, 1H, C5H4), 4.95 (m, 1H, C5H4), 5.01 (m, 1H, C5H4),
5.07 (m, 1H, C5H4), 5.13 (m, 1H, C5H4), 5.25 (m, 2H, C5H4),
5.33 (m, 1H, C5H4), 7.1–7.87 (m, 15H, Ph). 31P(1H), d: 33.4 (s,
1P, PPh2) ppm. 19F NMR, d: −124.3 (m, 1F, o-F), −123.0 (m,
1F, o-F), −122.3 (m, 1F, o-F), −121.1 (m, 1F, o-F), −154.7 [t,
3
3
1F, p-F, J(FF) 19.0 Hz], −154.4 [t, 1F, p-F, J(FF) 19.0 Hz],
−157.9 (m, 1F, m-F), −158.3 (m, 1F, m-F), −158.5 (m, 1F, m-F),
−158.7 (m, 1F, m-F).
1
data. H, d: 4.2–4.8 (m, br, 16H, C5H4), 7.1–7.8 (m, 30H, Ph).
31P(1H), d: 38.3 (s, 2P, PPh2, head to head isomer), 27.6 (s, 2P,
PPh2, head-to-tail isomer) ppm.
Synthesis of [Ag(OTf){Fc(EPh)PPh2}] (E = S (15), Se(16)).
To
a solution of [Fc(SPh)PPh2] (0.096 g, 0.2 mmol)
Synthesis of [Au(PPh3){Fc(SPh)PPh2}]OTf (10). To a so-
lution of [Fc(SPh)PPh2] (0.048 g, 0.1 mmol) in 20 mL
of dichloromethane was added [Au(OTf)(PPh3)] (0.061 g,
0.1 mmol) and the mixture was stirred for 15 min. Concentration
of the solution to ca. 5 mL and addition of diethyl ether (10 mL)
or [Fc(SePh)PPh2] (0.106 g, 0.2 mmol) in 20 mL of
dichloromethane was added [Ag(OTf)] (0.052 g, 0.2 mmol) and
the mixture was stirred for 30 min. Concentration of the solution
to ca. 5 mL and addition of diethyl ether (10 mL) gave complexes
15 or 16 as yellow or orange solids, respectively. Complex 15:
yield 71%. KM 4.5 X−1 cm2 mol−1. Elemental analysis (%), Found:
C, 46.88; H, 3.46; S, 7.97. Calc. for C29H23AgF3FeO3PS2: C,
1
gave complex 10 as a yellow solid. Yield 83%. NMR data. H,
d: 4.25 (m, 2H, C5H4), 4.39 (m, 2H, C5H4), 4.43 (m, 2H, C5H4),
4.82 (m, 2H, C5H4), 7.1–7.8 (m, 30H, Ph). 31P(1H), d: 42.7 (AB
system, 2P, PPh2 + PPh3, J(AB) 334) ppm.
1
47.37; H, 3.15; S, 8.72. NMR data. H, d: 4.33 (m, 4H, C5H4),
4.53 (m, 2H, C5H4), 4.64 (m, 2H, C5H4), 7.0–7.8 (m, 15H, Ph).
◦
31P(1H), −55 C, d: 5.2 (2d, 1P, PPh2, J(109AgP) 755, J(107AgP)
657 Hz) ppm. Complex 16: yield 83%. KM 1.6 X−1 cm2 mol−1.
Elemental analysis (%), Found: C, 44.18; H, 3.02; S, 4.22. Calc.
for C29H23AgF3FeO3PSSe: C, 44.53; H, 2.96; S, 4.09. NMR data.
1H, d: 4.51 (m, 4H, C5H4), 4.77 (m, 4H, C5H4), 7.4–7.6 (m,
15H, Ph). 31P(1H), −55 ◦C, d: 4.1 (2d, 1P, PPh2, J(109AgP) 695,
J(107AgP) 608 Hz) ppm.
Synthesis of [Au(C6F5)3{Fc(EPh)PPh2}] (E
=
S (11),
Se(12)). To a solution of [Fc(SPh)PPh2] (0.048 g, 0.1 mmol)
or [Fc(SePh)PPh2] (0.053 g, 0.1 mmol) in 20 mL of
dichloromethane was added [Au(C6F5)3(tht)] (0.078 g, 0.1 mmol)
and the mixture was stirred for 30 min. Concentration of the
solution to ca. 5 mL and addition of hexane (10 mL) gave
complexes 11 or 12 as yellow or orange solids, respectively.
Complex 11: yield 75%. KM 1.4 X−1 cm2 mol−1. Elemental
analysis (%), Found: C, 46.61; H, 1.99; S, 2.79. Calc. for
C46H23AuF15FePS: C, 46.96; H, 1.97; S, 2.72. NMR data. 1H, d:
4.04 (m, 2H, C5H4), 4.07 (m, 2H, C5H4), 4.19 (m, 2H, C5H4), 4.47
(m, 2H, C5H4), 6.96–7.80 (m, 15H, Ph). 31P(1H), d: 15.8 (s, 1P,
PPh2) ppm. 19F NMR, d: −122.0 (m, 2F, o-F), −120.1 (m, 4F, o-
F), −158.2 [t, 2F, p-F, 3J(FF) 19.8 Hz], −157.8 [t, 1F, p-F, 3J(FF)
19.9 Hz], −161.7 (m, 2F, m-F), −161.4 (m, 4F, m-F). Complex
12: yield 65%. KM 4.5 X−1 cm2 mol−1. Elemental analysis (%),
Found: C, 44.94; H, 1.81. Calc. for C46H23AuF15FePSe: C, 45.16;
Synthesis of [Ag{Fc(SPh)PPh2}2]OTf (17). To a solution of
[Fc(SPh)PPh2] (0.096 g, 0.2 mmol) in 20 mL of dichloromethane
was added [Ag(OTf)] (0.026 g, 0.1 mmol) and the mixture
was stirred for 30 min. Concentration of the solution to ca.
5 mL and addition of diethyl ether (10 mL) gave complexes
17 as a yellow solid. Yield 81%. KM 101 X−1 cm2 mol−1.
Elemental analysis (%), Found: C, 56.26; H, 3.51; S, 7.60. Calc.
for C57H46AgF3Fe2O3P2S3: C, 56.40; H, 3.82; S, 7.92. NMR
data. 1H, d: 4.20 (m, 2H, C5H4), 4.23 (m, 2H, C5H4), 4.28
(m, 2H, C5H4), 4.50 (m, 2H, C5H4), 7.0–7.5 (m, 30H, Ph).
31P(1H), −55 ◦C, d: 0.94 (2d, 1P, PPh2, J(109AgP) 471.3, J(107AgP)
410.4 Hz) ppm.
1
H, 1.89. NMR data. H, d: 4.01 (m, 4H, C5H4), 4.20 (m, 2H,
C5H4), 4.43 (m, 2H, C5H4), 7.50–7.80 (m, 15H, Ph). 31P(1H),
d: 15.9 (s, 1P, PPh2) ppm. 19F NMR, d: −122.5 (m, 2F, o-
F), −120.7 (m, 4F, o-F), −158.8 [t, 2F, p-F, 3J(FF) 19 Hz],
−158.5 [t, 1F, p-F, 3J(FF) 20 Hz], −162.4 (m, 2F, m-F), −162.1
(m, 4F, m-F).
Synthesis of [Ag(OTf)(PPh3){Fc(EPh)PPh2}] (E = S (18),
Se(19)). To a solution of [Fc(SPh)PPh2] (0.048 g, 0.1 mmol)
or [Fc(SePh)PPh2] (0.053 g, 0.1 mmol) in 20 mL of
dichloromethane was added the corresponding amount of
[Ag(OTf)(PPh3)] (0.052 g, 0.1 mmol) and the mixture was stirred
for 30 min. Concentration of the solution to ca. 5 mL and
addition of diethyl ether (10 mL) gave complexes 18, or 19
as yellow–orange solids. Complex 18: yield 83%. KM 15.2 X−1
cm2 mol−1. Elemental analysis (%), Found: C, 56.88; H, 4.21; S,
6.12. Calc. for C47H38AgF3FeO3P2S2: C, 56.58; H, 3.83; S, 6.21.
Synthesis of [Au2(C6F5)6{Fc(SePh)PPh2}] (13). To a so-
lution of [Fc(SePh)PPh2] (0.053 g, 0.1 mmol) in 20 mL
of dichloromethane was added [Au(C6F5)3(OEt2)] (0.154 g,
0.2 mmol) and the mixture was stirred for 30 min. Concentration
of the solution to ca. 5 mL and addition of hexane (10 mL)
gave complexes 13 as an orange solid. Yield 71%. KM 2.1 X−1
cm2 mol−1. Elemental analysis (%), Found: C, 40.38; H, 1.32.
Calc. for C64H23Au2F30FePSe: C, 40.0; H, 1.20. NMR data. 1H,
d: 3.71 (m, 1H, C5H4), 3.93 (m, 1H, C5H4), 4.01 (m, 2H, C5H4),
4.05 (m, 2H, C5H4), 4.11 (m, 2H, C5H4), 7.1–7.77 (m, 15H, Ph).
31P(1H), d: 14.6 (s, 1P, PPh2) ppm. 19F NMR, d: −122.5 (m, 1F,
o-F), −122.2 (m, 1F, o-F), −121.5 (m, 2F, o-F), −120.1 (m, 2F,
1
NMR data. H, d: 4.26 (m, 4H, C5H4), 4.3 3 (m, 2H, C5H4),
4.52 (m, 2H, C5H4), 6.9–7.5 (m, 30H, Ph). 31P(1H), AB system,
broad, dA, 7.9, dB, 3.0 ppm, JAB 127, J109AgP ∼ 522, J107AgP
∼ 453 Hz. Complex 19: yield 72%. KM 10.5 X−1 cm2 mol−1.
Elemental analysis (%), Found: C, 53.64; H, 3.66; S, 2.68. Calc.
for C47H38AgF3FeO3P2SSe: C, 54.04; H, 3.66; S, 3.07. NMR
1
data. H, d: 4.45 (m, 2H, C5H4), 4.60 (m, 2H, C5H4), 4.80 (m,
3
o-F), −157.5 [t, 2F, p-F, J(FF) 19.0 Hz], −157.4 [t, 1F, p-F,
2H, C5H4), 4.86 (m, 2H, C5H4), 6.9–7.8 (m, 30H, Ph). 31P(1H),
AB system, dA, 11.5, dB, 5.2 ppm, JAB 109, J109AgP 500, J107AgP
435 Hz.
3J(FF) 20.0 Hz], −155.9 [t, 1F, p-F, 3J(FF) 19.1 Hz], −155.6 [t,
2F, p-F, 3J(FF) 19.0 Hz], −161.4 (m, 1F, m-F), −161.1 (m, 2F,
m-F), −160.8 (m, 1F, m-F), −160.2 (m, 2F, m-F).
Synthesis of [Cu{Fc(EPh)PPh2}2]PF6 (E = S (20), Se(21)).
Synthesis of [Au(C6F5)2{Fc(SePh)PPh2}]ClO4 (14). To
To a solution of [Fc(SPh)PPh2] (0.096 g, 0.2 mmol)
a
solution of [Fc(SePh)PPh2] (0.053 g, 0.1 mmol) in
or [Fc(SePh)PPh2] (0.106 g, 0.2 mmol) in 20 mL of
dichloromethane was added [Cu(NCMe)4]PF6 (0.037 g,
0.1 mmol) and the mixture was stirred for 30 min. Concentration
of the solution to ca. 5 mL and addition of diethyl ether (10 mL)
20 mL of dichloromethane was added
a solution of
[Au(C6F5)2(OEt2)2]ClO4 (0.077 g, 0.1 mmol) in diethyl ether
and the mixture was stirred for 30 min. Concentration of the
D a l t o n T r a n s . , 2 0 0 5 , 3 0 0 5 – 3 0 1 5
3 0 1 3

View Article Online
gave complexes 20, or 21 as yellow–orange solids. Complex 20:
yield 80%. KM 98 X−1 cm2 mol−1. Elemental analysis (%), Found:
C, 57.63; H, 4.21; S, 5.62. Calc. for C56H46CuF6Fe2P3S2: C, 57.72;
H, 3.98; S, 5.50. NMR data. 1H, d: 3.70 (m, 1H, C5H4), 4.00 (m,
1H, C5H4), 4.43 (m, 5H, C5H4), 4.65 (m, 1H, C5H4), 7.1–7.5 (m,
30H, Ph). 31P(1H), d: −8.9 (s, 2P, PPh2) ppm. Complex 21: yield
83%. KM 106 X−1 cm2 mol−1. Elemental analysis (%), Found: C,
53.42; H, 3.65. Calc. for C56H46CuF6Fe2P3Se2: C, 53.42; H, 3.68.
NMR data. 1H, d: 3.79 (m, 2H, C5H4), 4.26 (m, 2H, C5H4), 4.33
(m, 2, C5H4), 4.46 (m, 1H, C5H4), 7.1–7.5 (m, 30H, Ph). 31P(1H),
d: −7.6 (s, 2P, PPh2) ppm.
(m, 2H, C5H4), 7.4–7.7 (m, 30H, Ph). 31P(1H), d: 28.3 (s, 2P, PPh2)
ppm.
Crystal structure determinations
Data were registered on a Siemens STOE AED-2 (4), Bruker
SMART 1000 CCD (3, 15, 18) or Bruker SMART APEX (5,
6, 16, 19) diffractometer. The crystals were mounted in inert
oil on glass fibres and transferred to the cold gas stream of
the corresponding diffractometer. Data were collected using
˚
monochromated MoKa radiation (k = 0.71073 A) in x-scan
mode or x and φ-scans (3, 15, 18). An absorption correction
was applied on the basis of φ-scans for 4 and of indexed faces
for 3, 15 and 18; otherwise the program SADABS, based on
multiple scans, was used. The structures were solved by direct
methods and refined on F2 using the program SHELXL-97.37
All non-hydrogen atoms were refined anisotropically (with the
exception of solvent of 4). Hydrogen atoms were included using
a riding model.
Synthesis of [AuAg{Fc(SPh)PPh2}2](ClO4)2 (22). To a solu-
tion of [Au{Fc(SPh)PPh2}2]ClO4 (0.125 g, 0.1 mmol) in 20 mL
of dichloromethane was added AgClO4 (0.021 g, 0.1 mmol)
and the mixture was stirred for 30 min. Concentration of the
solution to ca. 5 mL and addition of diethyl ether (10 mL)
gave complexes 22 as a yellow solid. Yield 81%.%. KM 153
X−1 cm2 mol−1. Elemental analysis (%), Found: C, 46.45; H,
3.36; S, 4.48. Calc. for C56H46AuAgCl2Fe2O4P2S2: C, 46.05; H,
1
3.17; 4.39. NMR data. H, d: 5.04 (br, m, 4H, C5H4), 5.26 (br,
Special features of refinement. For 3 the Flack parameter
was refined to −0.015(4). For complex 4 extensive regions of
badly resolved residual electron density could not be clearly
identified as disordered solvent molecules, so the main peaks
were refined as partially occupied carbons. For the calculation
of composition, etc., the solvent content was estimated as
half a hexane molecule per asymmetric unit. For 15 and
18 the asymmetric unit contains a dichloromethane molecule
disordered over an inversion centre. In 18 the triflate group is
disordered over two sites in the ratio 85 : 15. Suitable similarity
restraints were used to ensure stability of refinement. Further
crystal data are given in Tables 9 and 10.
m, 4H, C5H4), 6.7–7.5 (m, 30H, Ph). 31P(1H), d: 39.09 (s, 2P,
PPh2, head to head isomer, 97%), 30 (s, 2P, PPh2, head to tail
isomer, 3%) ppm.
Synthesis of [Au2PdCl4{Fc(EPh)PPh2}2] (23). To a solu-
tion of [Fc(SePh)PPh2] (0.106 g, 0.2 mmol) in 20 mL of
dichloromethane was added a solution of [PdCl2(NCPh)2]
(0.038 g, 0.1 mmol) and the mixture was stirred for 30 min.
Concentration of the solution to ca. 5 mL and addition of
hexane (10 mL) gave complex 23 as an orange solid. Yield 87%.
KM 1.8 X−1 cm2 mol−1. Elemental analysis (%), Found: C, 39.49;
H, 2.60. Calc. for C56H46Au2Cl4Fe2P2PdSe2: C, 39.73; H, 2.74.
NMR data. 1H, d: 4.46 (m, 3H, C5H4), 4.52 (m, 3H, C5H4), 4.81
CCDC reference numbers 272428–272435.
See http://dx.doi.org/10.1039/b507058a for crystallographic
data in CIF or other electronic format.
Table 9 X-Ray data for complexes 3, 4, 5 and 6
Compound
3
4·1/2C6H14
5
6
Formula
Mr
Habit
C28H23AuClFePS
710.76
Yellow plate
0.18 × 0.13 × 0.08
Orthorhombic
P212121
C37H30AuF5FePS
885.46
Yellow prism
0.49 × 0.27 × 0.23
Monoclinic
C2/c
C28H23AuClFePSe
757.66
Orange plate
0.28 × 0.12 × 0.04
Monoclinic
P21/c
C34H23AuF5FePSe
889.27
Orange prism
0.32 × 0.26 × 0.15
Triclinic
Crystal size (mm)
Crystal system
Space group
Cell constants:
P(−1)
˚
a/A
9.1540(8)
10.6559(8)
25.390(2)
90
90
90
2476.6(3)
4
1.906
6.7
31.212(6)
12.970(3)
22.518(5)
90
132.70(3)
90
6699(3)
8
1.756
4.97
10.0410(7)
22.0090(15)
11.8345(8)
90
106.220(1)
90
2511.2(3)
4
2.004
11.7891(5)
14.7442(6)
18.4764(8)
73.385(1)
84.788(1)
76.932(1)
2996.6(2)
4
˚
b/A
˚
c/A
a/◦
b/◦
c /◦
3
˚
V/A
Z
Dx/Mg m−3
1.971
6.7
l/mm−1
8.04
F(000)
1376
−130
57
3464
1448
1704
T/◦C
−100
−173
−173
2hmax
50
57.1
57.4
No. of refl.:
measured
independent
Transmissions
Rint
Parameters
Restraints
wR(F2, all Refl.)
R(F, >4r(F))
45484
6147
0.34 −0.73
0.081
298
7063
5916
0.69–0.76
0.026
413
16363
5936
0.21–0.73
0.066
298
20097
13522
0.22–0.43
0.039
775
92
85
0
0
0.043
0.023
0.980
0.74
0.082
0.034
1.007
1.01
0.076
0.040
0.824
1.8
0.096
0.042
0.933
2.1
S
−3
˚
Max. Dq (e A
)
3 0 1 4
D a l t o n T r a n s . , 2 0 0 5 , 3 0 0 5 – 3 0 1 5

View Article Online
Table 10 X-Ray data for complexes 15, 16, 18 and 19
Compound
15·1/4CH2Cl2
16
18·1/2CH2Cl2
19
Formula
Mr
Habit
C29.25H23.5AgCl0.5F3FeO3PS2
756.52
Yellow plate
0.48 × 0.24 × 0.04
Triclinic
C29H23AgF3FeO3PSSe
728.18
Orange prism
0.12 × 0.10 × 0.08
Triclinic
C47.5H39AgClF3FeO3P2S2
1040.02
Yellow plate
C47H38AgF3FeO3P2SSe
1044.45
Orange prism
0.18 × 0.18 × 0.10
Monoclinic
Crystal size (mm)
Crystal system
Space group
Cell constants:
0.33 × 0.23 × 0.07
Monoclinic
P(−1)
P(−1)
P21/n
P21/c
˚
a/A
11.5500(10)
12.6343(10)
19.8830(16)
87.345(3)
87.028(3)
80.112(3)
2852.4(4)
4
9.7756(9)
12.0232(11)
12.7493(12)
66.890(1)
86.717(2)
84.285(2)
1371.1(2)
2
10.7313(8)
18.2674(14)
22.6389(16)
90
97.837(3)
90
4396.5(6)
4
1.571
12.9511(14)
16.8249(19)
20.548(2)
90
106.689(3)
90
4288.8(8)
4
1.618
˚
b/A
˚
c/A
a/◦
b/◦
c /◦
3
˚
V/A
Z
Dx/Mg m−3
1.762
1.5
1.895
2.7
l/mm−1
1.06
1.82
F(000)
1514
772
2108
2096
T/◦C
−130
−173
−130
−173
2hmax
60.06
57.5
56.6
56.7
No. of refl.:
measured
independent
Transmissions
Rint
Parameters
Restraints
wR(F2, all Refl.)
R(F, >4r(F))
36536
16266
0.58–0.91
0.047
743
9061
6158
0.73–0.81
0.062
361
84636
10919
0.70–0.94
0.069
583
28043
10106
0.82–1.0
0.076
532
13
0
190
0
0.081
0.032
0.991
1.02
0.111
0.053
0.807
1.08
0.080
0.031
1.013
0.66
0.128
0.059
0.966
0.73
S
−3
˚
Max. Dq (e A
)
19 T. Y. Dong and C. K. Chang, J. Chin. Chem. Soc., 1998, 45, 577.
20 I. R. Butler, S. Mussig and M. Plath, Inorg. Chem. Commun., 1999,
2, 424.
Acknowledgements
We thank the Direccio´n General de Investigacio´n Cient´ıfica
y Te´cnica (No. BQ2001-2409-C02-C01), and the Fonds der
Chemischen Industrie for financial support.
21 A. Alexakis and C. Benhaim, Tetrahedron: Asymmetry, 2001, 12,
1151.
22 Y. Ito, M. Sawamura and T. Hayashi, J. Am. Chem. Soc., 1986, 108,
6405.
23 N. J. Long, J. Martin, G. Opromolla, A. J. P. White, D. J. Williams
and P. Zanello, J. Chem. Soc., Dalton Trans., 1999, 1981.
24 V. C. Gibson, N. J. Long, A. J. P. White, C. K. Williams, D. J. Williams,
M. Fontani and P. Zanello, J. Chem. Soc., Dalton Trans., 2002, 3280.
25 V. C. Gibson, N. J. Long, A. J. P. White, C. K. Williams and D. J.
Williams, Organometallics, 2002, 21, 770.
26 see for example: (a) E. M. Barranco, M. C. Gimeno, A. Laguna,
M. D. Villacampa and P. G. Jones, Inorg. Chem., 1999, 38, 702;
(b) M. C. Gimeno and A. Laguna, Gold Bull., 1999, 32, 90; (c) E. M.
Barranco, O. Crespo, M. C. Gimeno, A. Laguna, P. G. Jones and B.
Ahrens, Inorg. Chem., 1999, 38, 702; (d) E. M. Barranco, O. Crespo,
M. C. Gimeno, P. G. Jones, A. Laguna and C. Sarroca, J. Chem. Soc.,
Dalton Trans., 2001, 2523; (e) S. Canales, O. Crespo, A. Fortea, M. C.
Gimeno, P. G. Jones and A. Laguna, J. Chem. Soc., Dalton Trans.,
2002, 2250.
27 O. Crespo, M. C. Gimeno, P. G. Jones, A. Laguna and C. Sarroca,
Chem. Commun., 1998, 1481.
28 M. C. Gimeno, P. G. Jones, A. Laguna, C. Sarroca, M. J. Calhorda
and L. F. Veiros, Chem. Eur. J., 1998, 4, 2308.
29 G. Pilloni, B. Corain, M. Degano and G. Zanotti, J. Chem. Soc.,
Dalton Trans., 1993, 1777.
30 A. G. Osborne, R. H. Whiteley and R. E. Meads, J. Organomet.
Chem., 1980, 193, 345.
References
1 Ferrocenes, Homogeneous Catalysis, Organic Synthesis and Materials
Science, ed. A. Togni and T. Hayashi, VCH, Weinheim, Germany,
1995.
2 Metallocenes, ed. A. Togni and R. L. Halterman, VCH, Weinheim,
Germany, 1998.
3 N. J. Long. Metallocenes, An Introduction to Sandwich Complexes,
Blackwell Science, Oxford, UK, 1998.
4 I. Manners, Adv. Organomet. Chem., 1995, 37, 131.
5 I. Manners, Chem. Commun., 1999, 857.
6 Y. Zhu, O. Clot, M. O. Wolf and G. P. A. Yap, J. Am. Chem. Soc.,
1998, 120, 1812.
7 P. D. Beer, Acc. Chem. Res., 1998, 31, 71.
8 J. E. Kingston, L. Ashford, P. D. Beer and M. G. B. Drew, J. Chem.
Soc., Dalton Trans., 1999, 251.
9 C. Vale´rio, J. L. Fillaut, J. Rui, J. Guittard, J. C. Blais and D. Astruc,
J. Am. Chem. Soc., 1997, 119, 2588.
10 J. D. Carr, S. J. Coles, W. W. Hassan, M. B. Hursthouse, M. A. Malik
and J. H. R. Tucker, J. Chem. Soc., Dalton Trans., 1999, 57.
11 P. D. Beer, P. A. Gale and G. Z. Chen, J. Chem. Soc., Dalton Trans.,
1999, 1897.
12 P. D. Beer and P. V. Bernhardt, J. Chem. Soc., Dalton Trans., 2001,
1428.
´
31 R. Uson, A. Laguna and M. Laguna, Inorg. Synth., 1989, 26, 85.
13 A. C. Templeton, W. P. Wuelfing and R. W. Murray, Acc. Chem. Res.,
2000, 33, 27.
14 R. S. Ingram, M. J. Hostetler and R. W. Murray, J. Am. Chem. Soc.,
1997, 119, 9175.
´
´
´
32 R. Uson, A. Laguna, M. Laguna, J. Jimenez, M. P. Gomez, A. Sainz
and P. G. Jones, J. Chem. Soc., Dalton Trans., 1990, 3457.
33 R. Uson, A. Laguna, M. Laguna, J. Jimenez and E. Durana, Inorg.
´
´
Chim. Acta, 1990, 168, 89.
15 T. J. Colacot, Chem. Rev., 2003, 103, 3101.
16 R. C. J. Atkinson, V. C. Gibson and N. J. Long, Chem. Soc. Rev.,
2004, 33, 313.
´
34 M. Bardajı, O. Crespo, A. Laguna and A. Fisher, Inorg. Chim. Acta,
2000, 304, 7.
35 G. K. Anderson and M. Lin, Inorg. Synth., 1990, 28, 61.
17 J. A. Adeleke, Y. W. Chen and L. K. Liu, Organometallics, 1992, 11,
´
36 R. Uson and A. Laguna, Inorg. Synth., 1982, 21, 71.
2453.
37 G. M. Sheldrick, SHELXL-97, a program for crystal structure
18 J. A. Adeleke and L. K. Liu, J. Chin. Chem. Soc., 1992, 39, 61.
¨
refinement. University of Gottingen, Germany, 1997.
D a l t o n T r a n s . , 2 0 0 5 , 3 0 0 5 – 3 0 1 5
3 0 1 5